Detergents

ABSTRACT

The present invention provides dry, free-flowing detergents which contain chlorine donors and a fluorescent whitener the particles of which are encased by a water-soluble coating agent. The encased fluorescent whiteners have a greatly enhanced stability during the storage life of the detergent.

United States Patent 11 1 Lohmann et al.

1 Nov. 5, 1974' 1 1 DETERGENTS [75] Inventors: Frank Lohmann, Arlesheim,

Switzerland; Claude Eckhardt, Mulhouse, France; Karl Kleiber, Arlesheim,Switzerland [73] Assignee: Ciba-Geigy AG, Basel, Switzerland [22] Filed:June 19, 1972 [21] Appl. No.: 263,901

UNITED STATES PATENTS 3,401,123 9/1968 Brynko et al. 252/316 3,573,2113/1971 Zwcidler et a1 252/95 3,627,758 12/1971 Weber et a1 252/95 XR3,640,874 2/1972 Gray 252/95 3,646,015 2/1972 Hamilton 252/95 3,681,2488/1972 Gould et-al. 252/89 3,706,670 12/1972 Gray 252/95 I PrimaryExaminer-Mayer Weinblatt Attorney, Agent, or FirmJoseph G. Kolodny; Edw.McC. Roberts; Prabodh 1. Almaula [57] ABSTRACT The present inventionprovides dry, free-flowing de- I tergents which contain chlorine donorsand a fluorescent whitener the particles of which are encased by awater-soluble coating agent.

The encased fluorescent whiteners have a greatly enhanced stabilityduring the storage life of the detergent.

10 Claims, No Drawings DETERGENTS The use of detergent compositions andof washing liquors which contain chlorine donors is gaining increasingimportance, in particular for washing procedures at low temperatures.Since most detergents contain fluorescent whiteners, or the washingprocedures are carried out in the presence of fluorescent whiteners, itis essential that these whitening agents are suficiently stable towardssuch chlorine donors.

In order to simplify the washing procedure, these chlorine donors arebeing incorporated to an increasing degree into the detergent in theform of compounds which are stable when dry and only split off chlorinein the washing liquor. In a large number of fluorescent whiteners,especially those containing watersolubilising groups, it has beenobserved that these compounds become at least partially decomposed whenthe detergent is stored, despite the fact that they are sufficientlystable to chlorine in the washing liquor. Besides the stability tochlorine of fluorescent whiteners in the washing liquor, an additionalrequisite for their incorporation into detergents which contain chlorinedonors is that they must be stable in the said detergents during thestorage life of these latter.

From German Offenlegungsschrift 1.926.084 it is known to protectfluorescent whiteners from the detergent components by incorporatingthem in particles which effervesce in water. These effervescentparticles must be admixed dry with the detergent; however, this provesdisadvantageous in achieving a uniform distribution of the fluorescentwhitener in small concentratron.

It is also already known to coat water-insoluble fluorescent whitenerswith film-forming organic protective substances in order to prevent themfrom agglomerating over long periods of storage. Compared with thisknown procedure, the present invention is based on the quite differentproblem of protecting water-soluble fluorescent whiteners from attack bychlorine donors while retaining the direct incorporation of thefluorescent whitener into the detergent slurry.

The discovery has been made that it is possible to protect certaingroups of fluorescent whiteners, namely those from the series of thedistyryl-diphenyls and stylbylnaphthotriazoles, from attack by chlorinedonors if their particles are coated with a water-soluble polymer.Carboxyalkyl celluloses, chiefly carboxymethyl cellulose, have provedparticularly suitable for this purpose. In so doing, it was particularlysurprising that it is possible to protect water-soluble fluorescentwhiteners with a water-soluble polymer quite adequately, even on addingthe fluorescent whitener to the aqueous slurry.

Besides the preferred substances cited hereinbefore, it is also possiblein principle to use other organic, watersoluble polymeric substances ascoating agents, primarily those which liberate the coated fluorescentwhitener on introducing it into an aqueous alkaline medium within atmost about 5 minutes, but preferably within about 2 minutes. During thisprocess the weight ratio between fluorescent whitener and protectivesubstances may be between 9:1 and 1:99; but in general it is between 4:1and 1:4, preferably between 2:1 and 1:2.

Suitable substances of this kind are described e.g. in Water SolubleResins, byR. L. Davidson and Marshall Siftig, Reinhold Publ. Corp, NewYork, 1962.

mers of acetic acid vinyl ester and crotonic acid, also water-solublesalts of these polymeric acids, likewise water-soluble half esters and'their salts, polyacrylamide, polyvinyl alcohol, water-soluble starch orsugar, shellac, casein, polysulphone resins, polymers with structuralelements of the formula water-soluble urea/formaldehyde and melamine/formaldehyde condensation products, poly-[3,3'-methylimino-bis-trimethyleneadipic amide], polybenzooxazoles withstructural elements of the formula cellulose sulphate ester, polyvinylpipefidonqgelatin, pectin, heparin, alginic acid and its salts,polystyrenesulphonic acid, cyanoethyl cellulose, hydroxyalkyl cellulose.

Of industrial interest are coating agents from the group of thepolyvinyl pyrrolidones, polymers of acrylic and methacrylic acid andtheir esters and amide derivatives, styrene-maleic copolymers, polyvinylalcohols, water-soluble starches, water-soluble urea/formaldehyde andmelamine/formaldehyde condensation products, cellulose sulphate esters,carboxyalkyl cellulose, alginic acid and salts.

Preferred coating agents are, as already mentioned, carboxyalkylcelluloses, such as carboxymethyl cellulose; also suitable arehydroxyethyl celluloses and polyvinyl alcohol. The term hydroxyalkylcellulose is to be understood as meaning here in addition to thehydroxyalkyl cellulose in the narrow sense, e.g. hydroxypropyl celluloseor hydroxyethylhydroxypropyl cellulose, also the alkylhydroxyalkylcellulose, i.e., those cellulose ethers in which not all ethericallybonded alkyl radicals contain hydroxyl groups, where they arewater-soluble, thus, for example, water-soluble ethylhydroxyethylcelluloses, methylhydroxyethyl celluloses or methylhydroxypropylcelluloses. (Included in the term water-soluble are also substanceswhich form colloidal aqueous solutions).

The coating agents may be applied to the fluorescent whiteners singly orin admixture. Inaddition, they may contain additives, e.g. ionogenic ornon-ionogenic dis-t -persing agents or plasticisers.

Suitable fluorescent whiteners for the incorporation into the detergentsaccording to the invention are: I. Bis-stilbene compounds of the formulawherein R represents a sulpho group or the salts thereof, R representshydrogen, chlorine, methyl, methoxy or a sulpho group or the saltsthereof. R and R independently represent hydrogen, chlorine, methyl ormethoxy. Preferred compounds are those of the formula cw TT As activedetergents it is possible to use anionic, cationic, amphoteric andnon-ionogenic surfactants or mixtures of these surfactants. Anionicsurfactants are preferred.

The anionic surfactants comprise soaps and other carboxylates,derivatives of sulphur-oxyacids or phoswherein R and R independentlyrepresent hydrogen, chlorine, methyl or methoxy.

ll. Stilbylnaphthotriazoles of the formula wherein V, representshydrogen or a sulpho group or the salts thereof, V represents hydrogen,chlorine, a cyano group, a carboxyl group or a sulpho group or the saltsthereof, V represents hydrogen, methoxy or a sulpho group or the saltsthereof, and V, represents hydrogen or chlorine, with at least one ofthe substituents V to V, representing a sulpho group or the saltsthereof.

in addition to the fluorescent whitener sealed within the coating agentthe preparations according to the invention contain the conventionaldetergent constituents. Besides the active detergents (surfactants) itis possible to add e.g. builders, bleaching agents and specialadditives, such as wetting agents (e.g., polywaxes and polyglycols forincreasing the soil suspending power), supcrfatting agents, fungicidesand deodorants, also filler and the like.

As dry chlorine donors which release hypochlorite ions on contact withwater importance attaches primarily to heterocyclic N-chloroimides, suchas trichloroisocyanuric acid and dichloroisocyanuric acid and the saltsthereof, e.g. sodium or potassium tri- 0 chloroisocyanurate. However, itis also possible to use other imides, e.g. N-chlorosuccinimide, N-chlorophthalimide, l,3-dichloro-5,5- dimethylhydantoin etc., as well asother compounds which split off hypochlorite, e.g. trichloromelamine orN,N-dichlorobenzoylene-urea. lt is, of course, also possible to useinorganic salts of hypochlorous acid, such as lithium or calciumhypochlorite.

SO Na phorus-oxyacids, as well as compounds which contain nitrogen inthe hydrophilic group.

Water-soluble salts of higher fatty and resinic acids may be cited asexamples of soaps.

Derivatives of sulphur-oxyacids are mostly sulphates, such as sulphatesof higher alcohols or sulphonates, e.g. alkylbenzenesulphonates andolefin sulphonates.

Preferred derivatives of phosphorus-oxyacids are phosphates, wherease.g. disulphimide salts exemplify the type which contains nitrogen inthe hydrophilic groups.

The cationic surfactants comprise amines and their salts, for exampleN-Z-aminoethylstearylamine or N-2-aminoethylstearylamide,benzyl-dimethyl-stearylammonium chloride, trimethyl-cetyl-ammoniumbromide, etc., also onium compounds and amino oxides.

ethylene oxide adducts, for example isooctylphenol,

with about 8 to 30 ethylene oxide units.

Phosphates, in particular condensed phosphates, sili- 5 cates, borates,carbonates and organic builders, for example the salts ofnitrilotriacetic acid or ethylene-diamine-tetraacetic acid may be usedas water-soluble builders. In general, 0.5 to 10 parts of biulder areused to one part of surfactant (active detergent).

The detergents according to the invention are used chiefly for washingcotton fabrics. But they may also be used with advantage for cleansingtextiles made from other cellulose fibres, such as rayon, or otherfibres, such as synthetic polyamides, e.g., silk, wool, polyester,cellulose acetates, polyacrylonitrile, or mixtures of two or more ofthese types of fibre, e.g., cottonpolyester fibre fabrics.

As already mentioned, the stabilisation of the fluorescent whitener(s)is attained by coating it (or them) with one of the substances citedhereinbefore. This coatings is carried out by dissolving or dispersingthe fluorescentwhitener in an aqueous solution of the coating agent andthen evaporating this solution to dryness, for example by the spraydrying process. In this way there is first of all obtained a storabledry preparation which may then at any desired time be further processedto manufacture the detergents according to the invention.

To incorporate the fluorescent whitener into the detergent the proceduregenerally is that the fluorescent whitener obtained in the mannerdescribed hereinbefore is distributed as uniformly as possible in theslurry which, except for the chlorine donor and optionally perborate,contains all the constituents of the detergent. The amount offluorescent whitener to be pasted into the slurry is generally so fixedthat the detergent according to the invention contains 0.01 to 2,preferably 0.05 to 1 percent by weight thereof. The detergent slurry isthen dried, for example once more by spray drying. The end product isobtained by admixing the chlorine donor and optionally perborate withthe thus obtained dry preparation.

Example 1 A sodium carboxymethyl cellulose (62.5 g) with a low viscosityand an etherification degree of 0.8 is dissolved in 750 g of water. Thenthe sodium salt of 4,4- bis-(2-sulphostyryl)-diphenyl (62.5 g) is addedto the solution. This mixture is homogenised and spray dried. Theresulting dry preparation(4g) is then pasted into a slurry containing150 g of dodecylbenzenesulphonate, 100 g of sodium lauryl sulphonate,400 g of sodium tripolyphosphate, 255 g of calcined sodium sulphate, 70g of sodium metasilicate (9 hydrate), g of carboxymethyl cellulose and 5g of ethylenediamine-tetraacetic acid, and this mixture is then dried at90C. The resulting product is granulated and then mixed with 50 g oftrichloroisocyanurate.

Samples of the thus manufactured product are tested for their whiteningaction after 1, 7 and 30 days storage at room temperature.

The comparison is made with detergent samples of the above describedcomposition which have likewise been stored for l, 7 and 30 days and onthe one hand contain trichloroisocyanurate and on the other contain notrichloroisocyanurate, but into which the fluorescent whitener has beenintroduced without protective coating.

In addition to these comparative tests, cotton samquors each containing4 g of detergent/l at a liquor ratio of 1:20, the detergent having beenadded exactly 1 minute before the cotton was introduced. The degree ofwhiteness of the washed samples is determined by the Ciba WhitenessScala (cf. Journal of the Soc. Dyers and Col. 84, 1968, -132). Theresults are given in the following Table.

Table -1 Detergent Sample Degree of whiteness of cotton samples afterwashing with detergent stored for days Similar results are obtained byusing 4,4'-bis-(2- sulpho-5chloro-styryl)-diphenyl or its sodium saltinstead of 4,4'-bis-(2-sulphostyryl)-diphenyl.

Example 2 The process as described in Example 1 is carried out,

except that 37.5 g of FWA is treated with 87.5 g of sodium carboxymethylcellulose (CMC) and of this preparation 6.7 g is pasted into thedetergent slurry. The results are given in the following Table.

Table 11 Detergent Sample Degree of whiteness of cotton samples afterwashing with detergent stored for days detergent containing tri- Theprocess as described in Example 1 is carried out,

except that 87.5 g of FWA is treated with 37.5 g of CMC and 2.9 g ofthis preparation is pasted into the detergent slurry. The results aregiven in the following Table.

Table III Degreeof whiteness of cotton samples after washing withdetergentstored for days Detergent Sample detergent containingtrichloroisocyanurate and FWA 200 195 treated with CMC detergentcontaining trichloroisocyanurate and 197.5 15715 142.5

untreated FWA Example 4 The process described in Example 1 is carriedout, except that the sodium salt of 4-[naphtho-I.2,:4.5-triazolyl-(2)]-2-sulpho-stilbene is used as FWA and polyvinyl alcohol(Gohsenol CL 03) is used as coating agent and the fabric is washed at50C. The results are given in the following Table.

Table IV Degree of whiteness of cotton samples after washing withdetergent stored for days l 7 30 Detergent Sample detergent containingtrichloroisocyanurate and FWA 190 I75 165 treated with polyvinyl alcoholdetergent containing trichloruisocyanurate and 190 155 127.5

untreated FWA detergent with FWA I95 195 195 Example The processdescribed in Example 1 is carried out, except that the sodium salt of4-[naphtho-1,2:4,5- triazo1yI-( 2)]-2-sulphostilbene is used as FWA andpolyvinyl alcohol (Gohsenol GL O3) is used as coating agent andpolyamide samples (Bodanyl-Helanca) are washed with the detergentsamples at 30C The results are given in the following Table 5.

Table 5 Degree of whiteness of polyamide samples after washing withdetergent stored for days I 7 30 Detergent Sample detergent containingtri- The process described in Example 1 is carried out, except that thesodium salt of 4-(2-sulphostyryI)-4-(2- chlorostyryl)-diphenyl is usedas FWA and polyvinyl alcohol (Gohsenol GL O3), is used as coating agentand the fabric is washed at 50C. The results are given in the followingTable.

Table VI Detergent Sample Degree of whiteness of cotton samples afterwashing with detergent stored for days detergent containingtrichloroisocyanurate and FWA treated with polyvinyl alcohol detergentcontaining trichloroisocyanurate and untreated FWA detergent with FWA215 215 215 8 Example 7 The process described in Example I is carriedout, except that the sodium salt of 4-(2-sulphostyryI)-4'-(2-chlorostyryl)diphenyl is used as FWA and polyvinyl alcohol (Gohsenol GLO3) is used as coating agent and the polyamide samples (Bodanyl-Helanca)are washed with the detergent samples at 30C. The results are given inTable VII.

Table VII Degree of whiteness of polyamide samples washed with detergent stored for days I 7 Detergent Sample detergent containingtrichloroisocyanurate and FWA 187.5 167.5 152.5

treated with polyvinyl alcohol detergent containingtrichloroisocyanurate and un- 197.5 135 122.5

treated FWA detergent with FWA 212.5 212.5 212.5

Example 8 The process described in Example 1 is carried out, except that50 g of FWA is treated with g of hydroxycellulose (Klucel E) and 5 g ofthis product is pasted into the detergent slurry and the washing testsare carried out after 2 hours, 3 and 12 days. The results are given inthe following Table.

Table VIII Degree of whiteness of cotton samples after washing withdetergent stored for Detergent Sample 2 hrs. 3 days 12 days detergentcontaining trichloroisocyanurate and FWA 197.5 175 167.5 treated withhydroxyethyl cellulose detergent containing trichloroisocyanurate andun- 182.5 127.5 treated FWA detergent with FWA 225 225 225 We claim:

1. Dry, free-flowing detergent compositions consisting essentially of asurfactant, a chlorine donor which releases hypochlorite ions on contactwith water and a fluorescent whitener selected from the group consistingof a distyryldiphenyl whitener of the formula 9 wherein R represents asulpho group or the salts 4. Detergent compositions according to claim1, thereof, R represents hydrogen, chlorine, methyl, wherein thefluorescent whitener particles contain carmethoxy or a sulpho group orthe salts thereof, R and boxymethyl cellulose, hydroxypropyl celluloseor poly- R independently represent hydrogen, chlorine, methyl vinylalcohol as water-soluble organic coating agent. or methoxy andastilbylnaphthotriazole whitener of the 5 5. Detergent compositionsaccording to claim 1, formula wherein the weight ratio betweenfluorescent whitener D' CH=CH /N V1 v N wherein V, represents hydrogenor a sulpho group, or and coating agent is 4:1 to 1:4. the saltsthereof, V represents hydrogen, chlorine, a 6. Detergent compositionsaccording to claim 1, cyano group, a carboxyl group, or a sulpho groupor the which contain fluorescent whiteners of the formula salts thereof,V represents hydrogen, methoxy or a sulwherein R and R independentlyrepresent hydrogen,

pho group or the salts thereof, and V represents hydrochlorine, methylor methoxy.

gen or chlorine, with at least one of the substituents V 7. Detergentcompositions according to claim 1, V

to V, standing for a sulpho group or the salts thereof, which contain4-[naphtho-1,2:4,5-triazolyl-(2)]-2- the particles of which are encasedby a watersoluble orsulphostilbene as fl r t whit n ganic coating agent,the weight ratio between said fluo- 8. Detergent compositions accordingto claim 6,

rescent whitener and said water-soluble organic prowhich contain4,4-bis-(2-sulphostyryl)-diphenyl as flutecting agent being between 9:1and 1:99. crescent hit 2. Dry, free-flowing detergent compositionsaccord- 9. Detergents according to claim 6, which contain 4- ing toclaim 1, which contain an anionic surfactant as(2-sulphostyryl)-4-(2-chlorostyryl) diphenyl as fluoactive detergent,chlorine donors, and a fluorescent rescent whitener. whitener from theseries of the distyryldiphenyls and 10. A process for the manufacture ofproducts of the stilbylnaphthotriazoles which contains at least onesulcomposition cited in claim 1, wherein a solution or dispho group (orthe salts thereof) and the particles of persion of the fluorescentwhitener in an aqueous soluwhich are encased by a water-soluble coatingagent. tion of the coating agent is evaporated to dryness, the Detergentcompositions according to claim 1 resultlng dry preparation pasted intothe detergent wherein the fluorescent whitener particles contain car- 5Slurry whlch evaporated, and the resultmg P boxymethyl cellulose aswater-soluble organic coating i is option'flny granulated and theChlorine. onor m mixed therewith.

1. DRY, FREE-FLOWING DETERGENT COMPOSITIONS CONSISTING ESSENTIALLY OF ASURFACTANT, A CHLORINE DONOR WHICH RELEASES HYPOCHLORITE IONS ON CONTACTWITH WATER AND A FLUORESCENT WHITENER SELECTED FROM THE GROUP CONSISTINGOF A DISTYRLDIPHENYL WHITENER OF THE FORMULA.
 2. Dry, free-flowingdetergent compositions according to claim 1, which contain an anionicsurfactant as active detergent, chlorine donors, and a fluorescentwhitener from the series of the distyryldiphenyls andstilbylnaphthotriazoles which contains at least one sulpho group (or thesalts thereof) and the particles of which are encased by a water-solublecoating agent.
 3. Detergent compositions according to claim 1, whereinthe fluorescent whitener particles contain carboxymethyl cellulose aswater-soluble organic coating agent.
 4. Detergent compositions accordingto claim 1, wherein the fluorescent whitener particles containcarboxymethyl cellulose, hydroxypropyl cellulose or polyvinyl alcohol aswater-soluble organic coating agent.
 5. Detergent compositions accordingto claim 1, wherein the weight ratio between fluorescent whitener andcoating agent is 4: 1 to 1:4.
 6. Detergent compositions according toclaim 1, which contain fluorescent whiteners of the formula
 7. Detergentcompositions according to claim 1, which contain4-(naphtho-1'',2'':4,5-triazolyl-(2))-2-sulphostilbene as fluorescentwhitener.
 8. Detergent compositions accordinG to claim 6, which contain4, 4''-bis-(2-sulphostyryl)-diphenyl as fluorescent whitener. 9.Detergents according to claim 6, which contain4-(2-sulphostyryl)-4''-(2-chlorostyryl)-diphenyl as fluorescentwhitener.
 10. A process for the manufacture of products of thecomposition cited in claim 1, wherein a solution or dispersion of thefluorescent whitener in an aqueous solution of the coating agent isevaporated to dryness, the resulting dry preparation pasted into thedetergent slurry which is then evaporated, and the resulting product isoptionally granulated and the chlorine donor mixed therewith.